CN102618280A - Nanometer apatite probe mixed with rare earth ions and preparation method thereof - Google Patents
Nanometer apatite probe mixed with rare earth ions and preparation method thereof Download PDFInfo
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- CN102618280A CN102618280A CN2012100550572A CN201210055057A CN102618280A CN 102618280 A CN102618280 A CN 102618280A CN 2012100550572 A CN2012100550572 A CN 2012100550572A CN 201210055057 A CN201210055057 A CN 201210055057A CN 102618280 A CN102618280 A CN 102618280A
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- -1 rare earth ions Chemical class 0.000 title claims abstract description 50
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 50
- 229910052586 apatite Inorganic materials 0.000 title claims abstract description 39
- 239000000523 sample Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- VSIIXMUUUJUKCM-UHFFFAOYSA-D pentacalcium;fluoride;triphosphate Chemical compound [F-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O VSIIXMUUUJUKCM-UHFFFAOYSA-D 0.000 title abstract description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 60
- 238000000034 method Methods 0.000 claims abstract description 20
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 16
- 230000032683 aging Effects 0.000 claims abstract description 14
- 150000001875 compounds Chemical class 0.000 claims abstract description 14
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000011575 calcium Substances 0.000 claims abstract description 12
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 12
- 230000008569 process Effects 0.000 claims abstract description 11
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 8
- 229910002651 NO3 Inorganic materials 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 61
- 238000002156 mixing Methods 0.000 claims description 56
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 32
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 23
- 238000004090 dissolution Methods 0.000 claims description 23
- 239000000725 suspension Substances 0.000 claims description 22
- 229920000642 polymer Polymers 0.000 claims description 18
- 235000019441 ethanol Nutrition 0.000 claims description 17
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 239000003876 biosurfactant Substances 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 10
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical group [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims description 8
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 7
- 229910001424 calcium ion Inorganic materials 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 239000012046 mixed solvent Substances 0.000 claims description 7
- 150000003016 phosphoric acids Chemical class 0.000 claims description 7
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical group [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 4
- 239000012670 alkaline solution Substances 0.000 claims description 4
- 239000001110 calcium chloride Chemical group 0.000 claims description 4
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 4
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 claims description 4
- 229910000396 dipotassium phosphate Inorganic materials 0.000 claims description 4
- 235000019797 dipotassium phosphate Nutrition 0.000 claims description 4
- DVENVBCPDCQQGD-UHFFFAOYSA-N dysprosium(3+);trinitrate Chemical group [Dy+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O DVENVBCPDCQQGD-UHFFFAOYSA-N 0.000 claims description 4
- FCBUKWWQSZQDDI-UHFFFAOYSA-N rhamnolipid Chemical compound CCCCCCCC(CC(O)=O)OC(=O)CC(CCCCCCC)OC1OC(C)C(O)C(O)C1OC1C(O)C(O)C(O)C(C)O1 FCBUKWWQSZQDDI-UHFFFAOYSA-N 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical group [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 3
- 239000000920 calcium hydroxide Chemical group 0.000 claims description 3
- 229910001861 calcium hydroxide Chemical group 0.000 claims description 3
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 3
- 229940061607 dibasic sodium phosphate Drugs 0.000 claims description 3
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 3
- GAGGCOKRLXYWIV-UHFFFAOYSA-N europium(3+);trinitrate Chemical group [Eu+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GAGGCOKRLXYWIV-UHFFFAOYSA-N 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 3
- YJVUGDIORBKPLC-UHFFFAOYSA-N terbium(3+);trinitrate Chemical group [Tb+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YJVUGDIORBKPLC-UHFFFAOYSA-N 0.000 claims description 3
- LLZBVBSJCNUKLL-UHFFFAOYSA-N thulium(3+);trinitrate Chemical group [Tm+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O LLZBVBSJCNUKLL-UHFFFAOYSA-N 0.000 claims description 3
- MWKXCSMICWVRGW-UHFFFAOYSA-N calcium;phosphane Chemical compound P.[Ca] MWKXCSMICWVRGW-UHFFFAOYSA-N 0.000 abstract description 7
- 239000006185 dispersion Substances 0.000 abstract description 5
- 239000004094 surface-active agent Substances 0.000 abstract description 4
- 230000008901 benefit Effects 0.000 abstract description 3
- 238000004020 luminiscence type Methods 0.000 abstract description 2
- 239000002245 particle Substances 0.000 abstract description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 abstract 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 abstract 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 abstract 2
- 229910019142 PO4 Inorganic materials 0.000 abstract 1
- 125000000217 alkyl group Chemical group 0.000 abstract 1
- 229910052739 hydrogen Inorganic materials 0.000 abstract 1
- 239000001257 hydrogen Substances 0.000 abstract 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract 1
- 239000007788 liquid Substances 0.000 abstract 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 abstract 1
- 239000010452 phosphate Substances 0.000 abstract 1
- 238000002604 ultrasonography Methods 0.000 abstract 1
- 238000005406 washing Methods 0.000 abstract 1
- 239000000463 material Substances 0.000 description 12
- 239000002105 nanoparticle Substances 0.000 description 7
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 description 6
- 238000012544 monitoring process Methods 0.000 description 5
- 239000000839 emulsion Substances 0.000 description 4
- 229910052588 hydroxylapatite Inorganic materials 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 239000011435 rock Substances 0.000 description 4
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 229910052771 Terbium Inorganic materials 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 description 3
- 230000001988 toxicity Effects 0.000 description 3
- 231100000419 toxicity Toxicity 0.000 description 3
- 241000282326 Felis catus Species 0.000 description 2
- 239000003519 biomedical and dental material Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000006073 displacement reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000004530 micro-emulsion Substances 0.000 description 2
- 238000005424 photoluminescence Methods 0.000 description 2
- 230000035479 physiological effects, processes and functions Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 206010006956 Calcium deficiency Diseases 0.000 description 1
- 229910052693 Europium Inorganic materials 0.000 description 1
- 239000004606 Fillers/Extenders Substances 0.000 description 1
- 229910000673 Indium arsenide Inorganic materials 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- UHYPYGJEEGLRJD-UHFFFAOYSA-N cadmium(2+);selenium(2-) Chemical compound [Se-2].[Cd+2] UHYPYGJEEGLRJD-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000003759 clinical diagnosis Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000000645 desinfectant Substances 0.000 description 1
- 238000003745 diagnosis Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- GNBHRKFJIUUOQI-UHFFFAOYSA-N fluorescein Chemical compound O1C(=O)C2=CC=CC=C2C21C1=CC=C(O)C=C1OC1=CC(O)=CC=C21 GNBHRKFJIUUOQI-UHFFFAOYSA-N 0.000 description 1
- 238000000799 fluorescence microscopy Methods 0.000 description 1
- 239000007850 fluorescent dye Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- RPQDHPTXJYYUPQ-UHFFFAOYSA-N indium arsenide Chemical compound [In]#[As] RPQDHPTXJYYUPQ-UHFFFAOYSA-N 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- 239000002502 liposome Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000011858 nanopowder Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000002367 phosphate rock Substances 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 230000000176 photostabilization Effects 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
- 239000002096 quantum dot Substances 0.000 description 1
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
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Abstract
The invention discloses a nanometer apatite probe mixed with rare earth ions and a preparation method thereof. The method uses a high-speed dispersion machine and ultrasonic processing. In an ethanol/hydrosolvent system containing polyvinyl pyrrolidone (PVP) and a biological surfactant and with the potential of hydrogen (pH) controlled by alkyl liquid, rare earth nitrate and compound contain calcium, phosphate solution or phosphoric acid are fully mixed to form a sol system with the calcium phosphorus molar ratio to reach 1.6-1.7 to 1, and the nanometer apatite probe mixed with rare earth ions can be obtained by hydrothermal, ultrasound or magnetic field aging and washing. In a preparation process, apatite particles are controllable in shape and size and good in dispersion. The prepared apatite probe has the advantages of being good in biocompatibility, good in luminescence performance, stable in exciting light and the like. The method is simple in process, quick and convenient to operate and easy to popularize and apply.
Description
Technical field
The present invention relates to a kind of rare earth ion doped nano-apatite probe and preparation method thereof; Be specifically related to controlled rear-earth-doped nano-apatite probe of a kind of pattern in the organic solvent system of pbz polymer tensio-active agent and bio-surfactant and preparation method thereof, belong to biomedical material and optical function material technical field.
Background technology
Bioprobe is the most effectively means of biological stain and diagnosis, mainly contains two types at present, and one type is the organic fluorescence molecule; Like rhodamine; Resorcinolphthalein etc., but the fatal shortcoming of these organic molecules is photic shank colors, and promptly its fluorescence intensity is along with the prolongation of time is gone down very soon; Another kind of is novel semiconductor nanoparticle quantum dot probe; Like CdSe, CdS, ZnS, InP and InAs etc.; Compare with organic probe, their stability in coenocorrelation is higher, and stable fluorescence-emission can be provided; But Nano semiconductor has bio-toxicity, thereby is difficult to get into Application Areas.By contrast; Nanometer hydroxyapatite has excellent biological compatibility and structural stability, and has been widely used in technical field of biological material, therefore is expected to address this problem; But Win 40350 itself does not have tangible luminescent properties, thereby is difficult to monitor and diagnose.The luminescent material of doping with rare-earth ions preparation is fit to fluorescence imaging and monitoring owing to have that fluorescence lifetime is long, emission peak is narrow and luminosity such as the Stokes displacement is big.Therefore, prepare Win 40350 through doping with rare-earth ions and be expected to become the new bio probe that more corresponds to actual needs with luminescent properties.
So far, the research of the luminescent material of more existing rear-earth-doped apatite crystal structures both at home and abroad, but be limited to phosphor material powder mostly, and the research of bioprobe material is less.For example: Ling Li; Yukan Liu; Jinhui Tao; The hydroxide radical phosphorite nanocrystalline bioprobe [J] of a small amount of Tb surface-treated. Acta PhySico-Chimica Sinica C, (Surface Modification of Hydroxyapatite Nanocrystallite by a Small Amount of Terbium Provides a Biocompatible Fluorescent Probe [J]. Journal of Physics and Chemistry of Solids) 2008,112:12219 – 12224; This article adopts cats product CTAB auxiliary synthetic with the precipitator method, has obtained terbium doped HAP bioprobe with fluorescent characteristic through vacuum-drying then.The Chinese invention patent application number is 200810060400.6 to disclose " a kind of preparation method who carries out the hydroxyl apatite fluorescent nano-particle of finishing with Tb ", the HAP bioprobe of terbium finishing that has been additive preparation with CTAB.In addition; A. Doat etc.; Synthetic [J] with biological phosphorus lime stone nano particle bioprobe of luminescent properties. the solid state chemistry journal; (Synthesis of luminescent bioapatite nanoparticles for utilization as a biological probe [J]. Journal of Solid State Chemistry) 2004,177:1179 – 1187, this article have reported the adulterated calcium deficiency type of the europium that in 37 ℃ ethanol-water media, has synthesized weak percent crystallinity phosphatic rock; And confirm that it luminously has a photostabilization, is suitable for as bioprobe.
Though aforesaid method has been prepared the nano-apatite with luminescent properties, also have the problem of two aspects: the use that is cats product CTAB on the one hand possibly make the surface of nano-apatite have certain toxicity; Be that processes such as constant pressure and dry or vacuum-drying can make nanoparticle agglomerates to a certain extent on the other hand; Cause intergranular optical gradient phenomenon like this; And cause monitoring and Error Diagnostics, but the particle of reuniting is because size is bigger, is difficult to get into some cell; The cell monitoring be can not carry out, its performance and application therefore limited.
In addition, the method for preparing the nano-apatite probe does not at present almost relate to the pattern and the size control of probe, and the research of field of light emitting materials confirms that particulate pattern, size have bigger influence to the luminescent properties of material.For example: Bing Yan, Jianfeng Gu, solvent-thermal method synthesizes the controlled NH of pattern
4ZnPO
4: Eu
3+Submicron order fluorescent material and luminescent properties thereof, (Morphology controlled solvo-thermal synthesis and luminescence of NH
4ZnPO
4: Eu
3+Submicrometer phosphor [J]. Journal of Alloys and Compounds) 2009,479:536 – 540, this article have confirmed that granule-morphology has very big influence to the luminescent properties of fluorescent material.H.M.H. Fadlalla, ChengchunTang, the synthetic Ce of sol-gel method with photoluminescence performance
3+Activated Y
3Al
5O
12Nano-powder, (Sol – gel preparation and photoluminescence properties of Ce
3+-activated Y
3Al
5O
12Nano-sized powders [J]. Journal of Crystal Growth) 2009,311:3737 – 3741, this article have confirmed that also granule-morphology has very big influence to the material luminescent properties.
Vinylpyrrolidone polymer (PVP) is a kind of parents' water-soluble high-molecular compound; Characteristics with excellent dispersion properties, complex ability and chemicalstability; Be applied to the synthetic field of metal nano material as dispersion agent, template and properties-correcting agent at present, pattern and size that can well ground control nano particle.The characteristic of PVP is its excellent physiological compatibility; In synthetic macromolecule; PVP is so both water-soluble, the kind that is dissolved in most of organic solvent again seldom, it once was widely used in extender,plasma the earliest in World War II; Be widely used in medical disinfectant and medical auxiliary materials at present, comprised stablizer as injection etc.In addition; Novel bio-surfactant is the amphipathic molecule that integrates hydrophilic group and hydrophobic group structure by microorganisms; Compare with synthetic surfactant, have biodegradable, good biocompatibility, can tolerate advantages such as extreme temperature and extreme pH value, and it can form micella, bilayer liposome with concentration change in water or electrolyte solution; Layered liquid crystal equates state of aggregation, is therefore having broad application prospects aspect synthesizing in the regulation and control of nano material.Yet; People mainly concentrate on fields such as oil production, food, makeup, agricultural and environment protection to the interest of bio-surfactant at present, and the application of and biomedical sector synthetic in nano material to it does not give to understand fully and pay attention to.
Therefore; The nano-apatite of control synthesizing rare-earth ion doping in containing the ethanol/water solvent system of PVP and bio-surfactant; Be expected to solve the physiology toxicity problem that synthetic phosphatic rock is caused by conventional surfactants and organic solvent in emulsion, microemulsion and reversed-phase emulsion system; Simultaneously can regulate and control the pattern and the size of nano-apatite probe, and improve its dispersiveness, and not see relevant report at present basically.
Summary of the invention
The objective of the invention is to overcome in the prior art granule-morphology to the luminiferous influence of material; Through the while rapping plate effect of screening ability, dissemination and the good ethanol/water solvent system that contains PVP and bio-surfactant of biocompatibility; Improve and optimization technology; Thereby provide a kind of granule-morphology, size and crystallization degree controlled; Good dispersivity has rare earth ion doped nano-apatite bioprobe of good biocompatibility and preparation method thereof, realizes through following technical proposal.
A kind of preparation method of rare earth ion doped nano-apatite probe, through following each step:
A. at room temperature; With the mass ratio of Vinylpyrrolidone polymer and bio-surfactant is the blended solid of 0.5～10 ︰ 1; The volume ratio that joins absolute ethyl alcohol and water is in the ethanol/water mixing solutions of 0.1～9 ︰ 1; Simultaneously with ultrasonic dissolution, to Vinylpyrrolidone polymer and the total mass concentration of bio-surfactant in ethanol/water mixed solvent be 0.001～0.06g/mL, must the mixing solutions I;
B. get the mixing solutions I of steps A; Add calcium containing compound and rare earth nitrate, simultaneously with ultrasonic dissolution, to the volumetric molar concentration of calcium containing compound be 0.01～2mol/L; Rare earth ion is 0.005～0.1 ︰ 1 with the mol ratio of (rare earth ion+calcium ion), gets the mixing solutions II;
C. get the mixing solutions I of steps A, add phosphoric acid salt or phosphoric acid, simultaneously with ultrasonic dissolution, to the volumetric molar concentration of phosphoric acid salt or phosphoric acid be 0.006～1.2mol/L, the mixing solutions III;
D. be to mix under 5000～15000 rev/mins with step B and C gained mixing solutions II and mixing solutions III low whipping speed; Adding alkaline solution adjusting pH value simultaneously is 10～12; With supersound process 10 minutes, form the suspension system IV that contains rare earth ion doped nano-apatite colloidal sol again; Calcium phosphorus mol ratio reaches 1.6～1.7 ︰ 1 in this suspension system IV at this moment;
E. with the suspension system IV of step D under 20～200 ℃, through conventional ageing 24～36 hours, use deionized water wash again, then through centrifugal treating, promptly obtain rare earth ion doped nano-apatite probe.
The type of the Vinylpyrrolidone polymer in the said steps A is K15, K30, K60 or K90.
Bio-surfactant in the said steps A is Yelkin TTS or rhamnolipid.
Calcium containing compound among the said step B is nitrocalcite, calcium chloride or calcium hydroxide.
Rare earth nitrate among the said step B is europium nitrate, Terbium trinitrate, thulium nitrate or Dysprosium trinitrate.
Phosphoric acid salt among the said step C is Secondary ammonium phosphate, Sodium phosphate, dibasic or potassium hydrogenphosphate.
Alkaline solution among the said step D is ammoniacal liquor, Pottasium Hydroxide or sodium hydroxide solution.
Ageing among the said step D is that the suspension system IV is placed autoclave ageing, ultrasonic field or magnetic field ageing.
Said ultrasonic dissolution is under power is the condition of 20～100W, to carry out supersound process 10 minutes.
Another object of the present invention is to provide a kind of rare earth ion doped nano-apatite probe, is the rare earth ion doped nano-apatite probe that obtains through above-mentioned process step.
The present invention has following outstanding advantage compared with prior art:
(1) the present invention improves and has optimized technology, and controlled, the high dispersing of the pattern of phosphatic rock, size and crystallization degree in the preparation process has solved that art methods prepares that the nano-apatite probe is prone to reunite and the problem that causes monitoring and Error Diagnostics.It is controlled that the nano-apatite probe that adopts present method to prepare has granule-morphology, size and percent crystallinity, high dispersing, and good biocompatibility, and have characteristics such as optical stability and good luminous property;
(2) the present invention adopts and to contain the PVP with good biocompatibility and the ethanol/water solvent system of bio-surfactant; Thereby the effect that it can have template and dispersion agent concurrently through the ratio and the concentration of each component in the adjustment system has solved the physiology toxicity problem that synthetic phosphatic rock is caused by conventional surfactants and organic solvent in emulsion, microemulsion and the reversed-phase emulsion system;
(3) because the nanometer hydroxyapatite probe of the present invention's preparation can be realized granule-morphology, controllable size; And have that fluorescence lifetime is long, emission peak is narrow and luminosity such as the Stokes displacement is big; Therefore of many uses, be specially adapted to biomedical material and clinical diagnosis and monitoring field thereof;
(4) preparation technology of the present invention is simple, and is simple to operation, is easy to apply.
Description of drawings
Fig. 1 is the emmission spectrum figure of rare earth ion doped nano-apatite probe under the 394nm optical excitation of embodiment 1 preparation;
Fig. 2 is the X-ray diffractogram of the rare earth ion doped nano-apatite probe of embodiment 1 preparation;
Fig. 3 is the transmission electron microscope picture of the rare earth ion doped nano-apatite probe of embodiment 1 preparation.
Embodiment
Below in conjunction with embodiment, the present invention is done to specify further, but embodiment is not limited in this.
Embodiment 1
A. at room temperature; With the blended solid of 0.05g Vinylpyrrolidone polymer (K15) with 0.05g Yelkin TTS; The volume ratio that joins absolute ethyl alcohol and water is in the ethanol/water mixing solutions of 0.1 ︰ 1; Simultaneously under power is the condition of 20W, carried out ultrasonic dissolution 10 minutes, to Vinylpyrrolidone polymer and the total mass concentration of Yelkin TTS in ethanol/water mixed solvent be 0.001g/mL, must the mixing solutions I;
B. get the mixing solutions I of steps A; Add calcium hydroxide and europium nitrate; Simultaneously, power carried out ultrasonic dissolution 10 minutes under being the condition of 20W; Volumetric molar concentration to calcium containing compound is 0.01mol/L, and rare earth ion is 0.005 ︰ 1 with the mol ratio of (rare earth ion+calcium ion), gets the mixing solutions II;
C. get the mixing solutions I of steps A, add phosphoric acid, under power is the condition of 20W, carried out ultrasonic dissolution 10 minutes simultaneously, to the volumetric molar concentration of phosphoric acid be 0.006mol/L, the mixing solutions III;
D. be to mix under 5000 rev/mins with step B and C gained mixing solutions II and mixing solutions III low whipping speed; Adding ammoniacal liquor adjusting pH value simultaneously is 10; With supersound process 10 minutes, form the suspension system IV that contains rare earth ion doped nano-apatite colloidal sol again; Calcium phosphorus mol ratio reaches 1.67 ︰ 1 in this suspension system IV at this moment;
E. with the suspension system IV of step D under 100 ℃, placed the autoclave ageing 24 hours, use deionized water wash again, then through centrifugal treating, promptly obtain rare earth ion doped nano-apatite probe.
Embodiment 2
A. at room temperature; With the blended solid of 0.05g Vinylpyrrolidone polymer (K30) with 0.1g Yelkin TTS; The volume ratio that joins absolute ethyl alcohol and water is in the ethanol/water mixing solutions of 0.67 ︰ 1; Simultaneously under power is the condition of 50W, carried out ultrasonic dissolution 10 minutes, to Vinylpyrrolidone polymer and the total mass concentration of Yelkin TTS in ethanol/water mixed solvent be 0.0015g/mL, must the mixing solutions I;
B. get the mixing solutions I of steps A; Add nitrocalcite and Terbium trinitrate, under power is the condition of 50W, carried out ultrasonic dissolution 10 minutes simultaneously, to the volumetric molar concentration of calcium containing compound be 0.1mol/L; Rare earth ion is 0.01 ︰ 1 with the mol ratio of (rare earth ion+calcium ion), gets the mixing solutions II;
C. get the mixing solutions I of steps A, add Sodium phosphate, dibasic, under power is the condition of 50W, carried out ultrasonic dissolution 10 minutes simultaneously, to phosphatic volumetric molar concentration be 0.0625mol/L, the mixing solutions III;
D. be to mix under 8000 rev/mins with step B and C gained mixing solutions II and mixing solutions III low whipping speed; Adding sodium hydroxide solution adjusting pH value simultaneously is 10.5; With supersound process 10 minutes, form the suspension system IV that contains rare earth ion doped nano-apatite colloidal sol again; Calcium phosphorus mol ratio reaches 1.6 ︰ 1 in this suspension system IV at this moment;
E. with the suspension system IV of step D under 20 ℃, placed the ultrasonic field ageing 24 hours, use deionized water wash again, then through centrifugal treating, promptly obtain rare earth ion doped nano-apatite probe.
Embodiment 3
A. at room temperature; With the blended solid of 0.5g Vinylpyrrolidone polymer (K90) with 0.2g Yelkin TTS; The volume ratio that joins absolute ethyl alcohol and water is in the ethanol/water mixing solutions of 1 ︰ 1; Simultaneously under power is the condition of 60W, carried out ultrasonic dissolution 10 minutes, to Vinylpyrrolidone polymer and the total mass concentration of Yelkin TTS in ethanol/water mixed solvent be 0.007g/mL, must the mixing solutions I;
B. get the mixing solutions I of steps A; Add nitrocalcite and thulium nitrate, under power is the condition of 60W, carried out ultrasonic dissolution 10 minutes simultaneously, to the volumetric molar concentration of calcium containing compound be 0.5mol/L; Rare earth ion is 0.05 ︰ 1 with the mol ratio of (rare earth ion+calcium ion), gets the mixing solutions II;
C. get the mixing solutions I of steps A, add potassium hydrogenphosphate, under power is the condition of 60W, carried out ultrasonic dissolution 10 minutes simultaneously, to the volumetric molar concentration of phosphoric acid salt or phosphoric acid be 0.3mol/L, the mixing solutions III;
D. be to mix under 10000 rev/mins with step B and C gained mixing solutions II and mixing solutions III low whipping speed; Adding potassium hydroxide solution adjusting pH value simultaneously is 11; With supersound process 10 minutes, form the suspension system IV that contains rare earth ion doped nano-apatite colloidal sol again; Calcium phosphorus mol ratio reaches 1.67 ︰ 1 in this suspension system IV at this moment;
E. with the suspension system IV of step D under 200 ℃, placed the autoclave ageing 36 hours, use deionized water wash again, then through centrifugal treating, promptly obtain rare earth ion doped nano-apatite probe.
Embodiment 4
A. at room temperature; With the blended solid of 5g Vinylpyrrolidone polymer (K90) with 1g Yelkin TTS; The volume ratio that joins absolute ethyl alcohol and water is in the ethanol/water mixing solutions of 4 ︰ 1; Simultaneously under power is the condition of 100W, carried out ultrasonic dissolution 10 minutes, to Vinylpyrrolidone polymer and the total mass concentration of Yelkin TTS in ethanol/water mixed solvent be 0.06g/mL, must the mixing solutions I;
B. get the mixing solutions I of steps A; Add calcium chloride and Dysprosium trinitrate, under power is the condition of 100W, carried out ultrasonic dissolution 10 minutes simultaneously, to the volumetric molar concentration of calcium containing compound be 0.8mol/L; Rare earth ion is 0.05 ︰ 1 with the mol ratio of (rare earth ion+calcium ion), gets the mixing solutions II;
C. get the mixing solutions I of steps A, add Secondary ammonium phosphate, under power is the condition of 100W, carried out ultrasonic dissolution 10 minutes simultaneously, to phosphatic volumetric molar concentration be 0.47mol/L, the mixing solutions III;
D. be to mix under 12000 rev/mins with step B and C gained mixing solutions II and mixing solutions III low whipping speed; Adding sodium hydroxide solution adjusting pH value simultaneously is 11.5; With supersound process 10 minutes, form the suspension system IV that contains rare earth ion doped nano-apatite colloidal sol again; Calcium phosphorus mol ratio reaches 1.7 ︰ 1 in this suspension system IV at this moment;
E. with the suspension system IV of step D under 20 ℃, placed the ultrasonic field ageing 24 hours, use deionized water wash again, then through centrifugal treating, promptly obtain rare earth ion doped nano-apatite probe.
Embodiment 5
A. at room temperature; With the blended solid of 3g Vinylpyrrolidone polymer (K60) with the 0.3g rhamnolipid; The volume ratio that joins absolute ethyl alcohol and water is in the ethanol/water mixing solutions of 9 ︰ 1; Simultaneously under power is the condition of 20W, carried out ultrasonic dissolution 10 minutes, to Vinylpyrrolidone polymer and the total mass concentration of rhamnolipid in ethanol/water mixed solvent be 0.033g/mL, must the mixing solutions I;
B. get the mixing solutions I of steps A; Add calcium chloride and Dysprosium trinitrate, under power is the condition of 20W, carried out ultrasonic dissolution 10 minutes simultaneously, to the volumetric molar concentration of calcium containing compound be 2mol/L; Rare earth ion is 0.1 ︰ 1 with the mol ratio of (rare earth ion+calcium ion), gets the mixing solutions II;
C. get the mixing solutions I of steps A, add potassium hydrogenphosphate, under power is the condition of 20W, carried out ultrasonic dissolution 10 minutes simultaneously, to phosphatic volumetric molar concentration be 1.2mol/L, the mixing solutions III;
D. be to mix under 15000 rev/mins with step B and C gained mixing solutions II and mixing solutions III low whipping speed; Adding sodium hydroxide solution adjusting pH value simultaneously is 12; With supersound process 10 minutes, form the suspension system IV that contains rare earth ion doped nano-apatite colloidal sol again; Calcium phosphorus mol ratio reaches 1.67 ︰ 1 in this suspension system IV at this moment;
E. with the suspension system IV of step D under 50 ℃, place the magnetic field ageing 30 hours of 10T, use deionized water wash again, then through centrifugal treating, promptly obtain rare earth ion doped nano-apatite probe.
Claims (10)
1. the preparation method of a rare earth ion doped nano-apatite probe is characterized in that through following each step:
A. at room temperature; With the mass ratio of Vinylpyrrolidone polymer and bio-surfactant is the blended solid of 0.5～10 ︰ 1; The volume ratio that joins absolute ethyl alcohol and water is in the ethanol/water mixing solutions of 0.1～9 ︰ 1; Simultaneously with ultrasonic dissolution, to Vinylpyrrolidone polymer and the total mass concentration of bio-surfactant in ethanol/water mixed solvent be 0.001～0.06g/mL, must the mixing solutions I;
B. get the mixing solutions I of steps A; Add calcium containing compound and rare earth nitrate, simultaneously with ultrasonic dissolution, to the volumetric molar concentration of calcium containing compound be 0.01～2mol/L; Rare earth ion is 0.005～0.1 ︰ 1 with the mol ratio of (rare earth ion+calcium ion), gets the mixing solutions II;
C. get the mixing solutions I of steps A, add phosphoric acid salt or phosphoric acid, simultaneously with ultrasonic dissolution, to the volumetric molar concentration of phosphoric acid salt or phosphoric acid be 0.006～1.2mol/L, the mixing solutions III;
D. be to mix under 5000～15000 rev/mins with step B and C gained mixing solutions II and mixing solutions III low whipping speed; Adding alkaline solution adjusting pH value simultaneously is 10～12; With supersound process 10 minutes, form the suspension system IV that contains rare earth ion doped nano-apatite colloidal sol again;
E. with the suspension system IV of step D under 20～200 ℃, through conventional ageing 24～36 hours, use deionized water wash again, then through centrifugal treating, promptly obtain rare earth ion doped nano-apatite probe.
2. preparation method according to claim 1 is characterized in that: the type of the Vinylpyrrolidone polymer in the said steps A is K15, K30, K60 or K90.
3. preparation method according to claim 1 is characterized in that: the bio-surfactant in the said steps A is Yelkin TTS or rhamnolipid.
4. preparation method according to claim 1 is characterized in that: the calcium containing compound among the said step B is nitrocalcite, calcium chloride or calcium hydroxide.
5. preparation method according to claim 1 is characterized in that: the rare earth nitrate among the said step B is europium nitrate, Terbium trinitrate, thulium nitrate or Dysprosium trinitrate.
6. preparation method according to claim 1 is characterized in that: the phosphoric acid salt among the said step C is Secondary ammonium phosphate, Sodium phosphate, dibasic or potassium hydrogenphosphate.
7. preparation method according to claim 1 is characterized in that: the alkaline solution among the said step D is ammoniacal liquor, Pottasium Hydroxide or sodium hydroxide solution.
8. preparation method according to claim 1 is characterized in that: the ageing among the said step D is that the suspension system IV is placed autoclave ageing, ultrasonic field or magnetic field ageing.
9. preparation method according to claim 1 is characterized in that: said ultrasonic dissolution is under power is the condition of 20～100W, to carry out supersound process 10 minutes.
10. by the prepared rare earth ion doped nano-apatite probe of arbitrary preparation method in the claim 1～9.
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| CN101153288A (en) * | 2007-09-29 | 2008-04-02 | 华南理工大学 | Microorganism catalytic synthesis process for mesoporous nano powder body hydroxyapatite |
| CN102249205A (en) * | 2011-05-06 | 2011-11-23 | 清华大学 | Rare earth doped hydroxyfluorapatite monocrystal nanometer wire and preparation method thereof |
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| CN101153288A (en) * | 2007-09-29 | 2008-04-02 | 华南理工大学 | Microorganism catalytic synthesis process for mesoporous nano powder body hydroxyapatite |
| CN102249205A (en) * | 2011-05-06 | 2011-11-23 | 清华大学 | Rare earth doped hydroxyfluorapatite monocrystal nanometer wire and preparation method thereof |
| CN102335142A (en) * | 2011-10-25 | 2012-02-01 | 上海理工大学 | Composite microspheres of nano liposome capable of being automatically assembled into insoluble medicament in situ and preparation method for composite microspheres |
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